Safetygram 30

Handling liquefied compressed gas

A liquefied compressed gas can be defined as a gas, which when compressed in a container, becomes a liquid at ordinary temperatures and at pressures ranging from 25 to 2500 psig. Liquefied gases have boiling points that range from
130F to 30F (90C to 1C). At 70F (21.1C) the cylinder contains both liquid and gas. Cylinder pressure, or the vapor
pressure of the gas, is directly affected by ambient temperature. Increases or decreases in the temperature will cause
the vapor pressure to increase or decrease, respectively.
Liquefied gases are packaged under their own vapor pressure and are shipped under rules that limit the maximum
amount that can be put into a container to allow for liquid expansion with rising temperatures. (The various transportation regulatory agencies have established very detailed requirements for the filling limits of liquefied compressed
gases to prevent the possibility of container overpressurization. Consult the regulations for your region for more
information.)
Typical liquefied compressed gases are listed in Table 1.

Containers
Liquefied compressed gases come in a variety of containers.
Because the product exists in both the liquid and gas phases in the container,
many containers are equipped to access both phases. This is accomplished by
the use of full-length eductor tubes (dip tubes) and gooseneck eductor tubes
(see Fig. 1).
Cylinders with a full-length eductor tube, or what is sometimes called a fulllength dip tube, have a tube that runs from the inlet of the cylinder valve to
the bottom of the cylinder. When a cylinder with this valve configuration is in
the upright position, the inlet of the tube is immersed in liquid, and the liquid
phase will be removed.
Some cylinders are equipped with two valves: one having a full-length eductor tube for liquid withdrawal and the other a valve without an eductor tube
for gas withdrawal or inert gas padding (see Fig. 2 and section on liquid-phase
withdrawal).
Another type of valve configuration is called the gooseneck eductor tube. The
gooseneck goes only a short distance into the cylinder and then bends to the
cylinder side opposite the valve outlet. In the upright position, the gooseneck
is above the liquid level and provides gas. To remove the liquid, the cylinder is
placed on its side with the valve outlet facing up. This puts the gooseneck into
the liquid.

Figure 1:

Figure 2:

Gas

Gas
Withdrawal
Valve
Liquid
Withdrawal
Valve

Liquid

Gas

Liquid

(left) Cylinder with gooseneck dip tube. (right)

Cylinder with full-length dip tube.

Some cylinders are equipped with two valves, one

with and one without an eductor tube.

In larger horizontal containers, such

as high pressure Y cylinders, low
pressure ton containers (multi unit
tank car tank), and tube trailers (see
Figs. 3, 4, and 5), dip tubes are required
to access both the liquid and gas
phases.

can be withdrawn from the rear of

the trailer with all dip tubes oriented
upward (to the vapor phase). Liquid
can be withdrawn from the front of
the trailer where the dip tubes will
be oriented downward into the liquid
phase.

Y cylinders use what is referred to as

a C configuration. This configuration
is very similar to the gooseneck, but
the inlet to the gooseneck is oriented
in the same direction as the valve
outlet. The product flows into the
dip tube and out the valve outlet in
a flow path shaped like the letter C.
This means when the valve outlet is
pointed up, the gas phase is accessed,
and when the valve outlet is pointed
down, the liquid phase is accessed.

The most common type of liquefied

gas container uses a standard cylinder valve. In the upright position the
liquid level is well below the valve
inlet, preventing liquid from being removed. If liquefied gas is to be
withdrawn, the bottom of the cylinder
must be elevated above the valve to
allow the liquid phase to be in contact
with the valve inlet. Special inversion
racks are usually used to provide a
safe method for cylinder inversion.

Ton containers have two valves. The

container is oriented so the valves
are one above the other. The valves
are connected to dip tubes that run to
the cylinder sides. The top valve will
have the dip tube in the vapor, and the
bottom valve will have the dip tube in
the liquid.
On tube trailers with liquefied compressed gases, gooseneck dip tubes
are used, but the dip tube orientation
is determined by the end of the tube
trailer that is being accessed. Typically
all valve outlets will be aimed downward on a tube trailer. Normally, gas

Table 1: Some Common Liquefied Gases*

Gas

Vapor Pressure @ 70F (21.1C)

Ammonia

114 psig (7.76 atm)

Carbon Dioxide

830 psig (56.5 atm)

Chlorine

86 psig (5.85 atm)

Hydrogen Chloride

613 psig (41.7 atm)

Hydrogen Sulfide

247 psig (16.8 atm)

Methyl Chloride

59 psig (4.01 atm)

Monomethylamine

44 psig (2.99 atm)

Nitrous Oxide

745 psig (50.7 atm)

Sulfur Dioxide

34 psig (2.31 atm)

Sulfur Hexafluoride

298 psig (20.3 atm)

Tungsten Hexafluoride

2.5 psig (0.17 atm)

Product withdrawal should be carefully supervised by qualified people

with the proper equipment. Personnel
should be aware of the associated
hazards of the product and equipment
and thoroughly understand applicable
safety regulations and emergency
procedures.

* Liquid petroleum gases, such as propane and butane, have not been included as they are too
numerous to mention.

Figure 3

There are two different methods of

product withdrawal from a liquefied
compressed gas container: as a vapor
(gas) or as a liquid (liquefied gas).

Vapor-phase withdrawal

Figure 4
Pressure Relief Device
Valve

Dip Tubes

Y cylinders use a C configuration dip tube.

How to withdraw product

safely

Valve
Pressure Relief Device

Ton containers have two valves, each

connected to a dip tube.

Liquefied compressed gases in a cylinder or any container exist in liquid

and gaseous form at a pressure equal
to the vapor pressure of the particular gas (see Table 1 for specific vapor
pressures). The cylinder pressure will
remain constant at the vapor pressure of the material as long as there is
any liquid remaining in the cylinder.
When the contents of the cylinder are
withdrawn to the point that no liquid
remains, the pressure in the cylinder
will begin to diminish as the remaining vapor is used.
The first step for removing vapor is to
orient the package to access the vapor
phase of the product.

Figure 5
Cylinder End Plug
5

10 /8" Radius
1

22 /2"
Length
Approx.

20" Radius
Approx.

22" O. D. Tube
1/2" Approx.

Dip Tube

Tube trailer front dip tube configuration.

When vapor is removed from the cylinder, the temperature and pressure
equilibrium is disturbed, and both
will decrease. Liquid will vaporize to
replace the gas that was removed, absorbing the heat of vaporization from
the remaining liquid and the container. This heat can usually be recovered
from the ambient air surrounding the
cylinder. If the withdrawal rate of the
gas is such that the energy required to
vaporize the liquid cannot be recovered from the surrounding air, the
liquid phase will begin to cool.
The phase equilibrium is a function of the system temperature. As
the temperature of the liquid phase
increases, so will the vapor pressure;
the converse is also true. If the liquid
cannot recover enough heat from its
surroundings to keep up with the
demand for gas, the liquid will cool.
This is called sub-cooling or autorefrigeration. It is common for vapor
withdrawal to cool the cylinder to the
point where moisture condenses on
the external cylinder, valve, and piping surfaces. If the surfaces are chilled
below waters freezing point, the condensed moisture can solidify into ice.
If the rate of withdrawal of vapor is
excessive, serious safety problems
can arise. Sub-cooling can cause the
vapor pressure to collapse to the point
where the cylinder pressure is below
that of the process. This pressure
inversion can cause backflow of the
process materials into the cylinder, or
suckback. It is also possible to cool a
cylinder enough to actually embrittle
the metal, potentially leading to a
cylinder failure. Ice formation on the
cylinder and especially on the valve
and piping, coupled with the decrease
in flow as the cylinder pressure drops,
is sometimes misinterpreted as blockage in the valve. This can lead to users
applying excessive heat to the valve,
possibly creating leakage at the outlet

Special warnings regarding vapor-phase

withdrawal
CAUTION! EXCESSIVE TEMPERATURE CONSIDERATIONS: Any enhanced
vapor withdrawal method listed here that involves heating should be
controlled to prevent exposure of the container to temperatures exceeding 125F (52C).
DANGER: Never heat an aluminum cylinder with electrical resistance
elements. Only cylinders made of steel should be electrically heated.
Aluminum cylinders can be severely damaged by excessive temperature
exposure.
CAUTION! ELECTRICAL REQUIREMENTS: All electrical systems for indirect heating and monitoring for a flammable gas supply system should
be designed to comply with the applicable national or local electrical
code requirements. Typical electrical code requirements include classification for instruments and/or limiting the surface temperature of heated
resistance elements to a specified fraction of the autoignition temperature for the flammable gas.
AIR PRODUCTS POSITION ON CODES: Various national and/or local
codes prohibit the general direct heating of containers. However, these
codes are interpreted as only pertaining to heating systems that apply
heat energy directly onto the containers.
This interpretation is based on the examples of prohibited heating methods cited in various code references: radiant flame, steam impingement
on the container, immersion in a heated water bath or electrical resistance heater elements in direct contact with the container.
Nonheated, flow-enhancing options should be evaluated as a first
preference. If none are suitable, a properly engineered and approved
INDIRECT heating system is acceptable for liquefied compressed gas
containers. Direct heating methods such as flames, steam impingement,
electrical resistance elements, water bath immersion, hot plates, and
ovens should not be used.
Water-bath immersion is not recommended: The direct immersion of a
cylinder into a water bath is NOT RECOMMENDED as a heating method,
since repeated or prolonged exposure to heated and agitated water can
degrade the cylinders external surface and can eventually compromise
the cylinders mechanical integrity. Use of acidic or alkaline water or the
use of conditioning salts and other materials has caused cylinder failures
when used in water baths.

connection, the valve packing, and

especially from a fusible metal relief
device if the valve is so equipped.

How can one improve the

gas-phase withdrawal
rate?

Depending on the cylinder or container geometry and ambient conditions,

some method might be necessary to
enhance product withdrawal from
liquefied compressed gas cylinders to
maintain required flow rates. This is
especially true with small cylinders
and nearly empty larger containers.
Product withdrawal enhancement
methods have a definite preference
of selection based on inherent safety
considerations and consequences of
system failure. This Safetygram presents the recommended methods in
order of preference and their associated requirements.
1. Use a Larger Container: This will
increase the outer surface area
of the container to allow more
heat transfer from the
environment.
2.

Vaporization: The user can with-

draw liquid phase through an
external vaporizer, thereby
converting the liquid to gaseous
product. This is the preferred
method for high flow requirements. This method requires
liquid-phase withdrawal from the
container using an eductor tube.
The liquid is then vaporized via
a standard vaporizer, tubing coil,
or other vaporization means. This
method can provide the highest
withdrawal rates, but may not be
suitable for high-purity applications. It also creates the highest release flow rate potential due
to downstream leakage or operator error, which should be
adequately addressed for hazard

ous products. Overpressure protec tion should be provided on any

lines, including the vaporizer
circuit, in which liquid product can
be trapped by isolation valves,
check valves, or other system
components.
3. Container Switching: This method
uses two or more identical con tainers or banks of containers
that can be switched to the online
position either manually or auto matically. When the primary,
active container vapor pressure
drops below the threshold capable
of supplying the desired gaseous
flow rates, the secondary, alternate
container is brought online in
place of the previously active con tainer. This permits the first
container to rewarm by absorbing
ambient heat. The switching
sequence is repeated throughout
the high flow demand. This
method may not be feasible if the
ambient temperature conditions
do not provide adequate heat to
rewarm the off-line container
within an acceptable period of
time.

Warning: Manifolding liquefied

compressed gas cylinders, together
without good engineering practices to
prevent product migration of one cylinders contents into another cylinder,
may result in:
1. Container rupture.
2. Major property damage.
3. Serious injury or death.
4. Noncompliance with local,
national or international shipping
and fire/occupancy regulations.
CAUTION, Cylinder Heating
Considerations: Any equipment used
to heat a cylinder of liquefied compressed gas must include redundant
over-temperature protection, such
as a system temperature controller (thermostat) with a maximum
setpoint of 125F (52C) along with a
separate, independent overtemperature shutdown device, such
as a fusible link, in the power supply
to the heater. The over-temperature
shutdown must be installed between
the heat source and the cylinder.

5.

4. Container Manifolding:
Manifolding a number of liquefied,
compressed gas containers in par-

allel permits the user to achieve

the required gaseous flow rate by
withdrawing product from all con-

tainers simultaneously. This

method benefits from the larger

thermal mass of the manifolded
cylinders and product and provides

additional container surface

area for ambient heat transfer,

thus enhancing total gaseous

withdrawal capability. However,
manifolding may not be adequate
if ambient temperature conditions
do not yield sufficient heat flow or
product vapor pressures within
the containers.

Convective Conditioning:
Gas withdrawal can be enhanced
by heating the atmosphere sur -
rounding the container to provide
additional thermal convective
heating of the containers and their
contents to increase product vapor
pressure. This approach is best
accomplished if the container is
held within an enclosure or
small room and it provides
gradual, controlled heating of the
container contents. However, this
system may not prove feasible for
containers located outdoors,
within a large room, or in a highly
ventilated/exhausted enclosure.

6. Radiant Conditioning: Heat lamps

(or equal) can be used to provide
radiant heating of the container
contents to increase container
pressure for enhanced gas with-
drawal capability. The heat source
must not directly heat the contain-
er valve since the valve, connec-
tion, and relief device components
can be damaged by excessive
temperatures. This method is best
utilized for indoor systems with
no obstructions around the
containers and provides gradual
heating of the container contents.
The system may not be feasible
for containers located outdoors or
in congested areas.
7.

Temperature-Controlled Jacket:
This method encloses the container in a removable, temperaturecontrolled jacket that contains
a closed-loop, recirculated heat
transfer fluid connected to a
separate electric heater unit. This
design separates the heating
element from the container and
also allows for heating or cooling the containers, depending on
the process pressure requirements.
The electric heater should have a
heat output rated for the maximum product withdrawal rate
requirements, without excessive
overcapacity. This design is widely
used for multiple container systems where there is sufficient
space to locate the heating unit
adjacent to the containers.

8. Electrically Heated Blanket: The

container can be encased in a
removable blanket that contains
electrically heated resistance
elements operated by a tempera-
ture controller. Blankets should
have an integral covering perma-
nently attached to their inner sur-
face to prevent direct contact of
the heating elements with the
container. The power input to the
blanket should be limited, based
on maximum withdrawal rate
requirements to restrict worst case heat input to the container
during temperature controller
runaway.

Liquid-phase withdrawal

Just as in vapor-phase removal, the

first step in liquid-phase removal is to
orient the package to gain access to
the liquid phase. The liquid is pushed
from the cylinder by the vapor pressure of the product. As the liquid is
removed, it increases the volume of
the vapor space of the cylinder. Some
liquid will vaporize to fill the additional space, but usually not enough
to excessively sub-cool the cylinder.
Sometimes the vapor pressure of the
product is not high enough to push
the liquid out at the required rate.
When this is the case, a method called
padding can be used to pressurize
the liquid. This enhances the rate at
which the liquid can be pushed from
the cylinder. Padding is the addition
of an inert gas to the vapor space in
the cylinder to raise the cylinder pressure. When adding the inert gas to the
cylinder, the cylinder pressure rating
must never be exceeded. This pressure
rating is part of the regulatory stamping on the cylinder. The maximum allowable working pressure (MAWP) of
the cylinder is stamped into the cylin-

der. In the United States the stamping

may read DOT3AA480, where 480 psig
is the MAWP. In Europe the stamping may read FP25BAR, where 25 BAR
is the MAWP. Furthermore, certain
cylinder relief devices may vent the
cylinder contents at pressures below
the pressure rating of the cylinder. If
you are not sure how to interpret the
DOT stamping, or for guidance concerning padding a cylinder, contact
your supplier.
How the inert gas pressure is added
depends upon the cylinder. If the
cylinder has dual valves, the inert gas
can be added through the gas-phase
valve. Be sure the inert gas source is
regulated to not exceed the pressure
rating of the cylinder and is protected
from backflow minimally by a check
valve. If the cylinder has one valve,
the inert gas can be added while the
cylinder valve is oriented to the vapor
phase, then the inert gas source can
be disconnected before orienting to
the liquid phase. Again, care must be
taken not to exceed the pressure rating of the cylinder. Some applications
use air in place of the inert gas for
padding. For some products, unloading with air padding may be prohibited by regulations. NEVER USE AIR TO
PAD FLAMMABLE PRODUCTS. When
air padding is allowed and appropriate, it is imperative that clean, oil-free,
cooled, dry compressed air be introduced into the vapor space through
its vapor valve to transfer the liquid.
NEVER use a plant air system for air
padding since vapors may backflow
into the plant air system.

Extreme care must be taken when

handling the liquid phase of any liquefied compressed gas. Unlike gas, the
liquid does not compress. Therefore,
the liquid must always have a space
to expand, especially as it warms. In
the cylinder, this expansion space is
provided by the vapor space or head
space.
The filling limits/fill density for liquefied compressed gases were described
earlier. These limits were set to
prevent the cylinder from becoming
liquid full at normal storage and use
temperatures. If a vessel or system
becomes liquid full, any increase in
temperature would cause the liquid
to try to expand with no space for the
expansion. The liquids incompressibility would result in a rapid increase
of hydrostatic pressure. These pressures can build very rapidly and can
quickly cause overpressurization of
the equipment. Overpressurization of
a system takes place when its pressure rating is exceeded. This can result
in a rupture of the system. Systems
using liquefied gases as liquids should
be adequately protected by pressure
relief devices, especially where there
is a chance to trap liquid between
valves or in other components that
can be isolated.

Important considerations
1.

NEVER allow any part of a

liquefied gas container to be
exposed to temperatures greater
than 125F (51C).

2. NEVER fill any cylinders without

the owners written consent.
3. NEVER heat an aluminum cylinder
with electrical resistance heaters.
4. ALWAYS refer to the Material
Safety Data Sheet for specific
chemical properties.

Manufacturers of systems
to enhance withdrawal
rates
Consult the Thomas Register to locate
vendors of cylinder heating systems or vaporizers. Or contact the
Air Products Gases and Equipment
Technical Information Center at
+1-800-752-1597.

Emergency Response System

T 800-523-9374 (Continental U.S. and Puerto Rico)
T +1-610-481-7711 (other locations)
For regional ER telephone numbers, please refer to the local SDS 24 hours a day, 7 days a week
for assistance involving Air Products and Chemicals, Inc. products

Technical Information Center

T 800-752-1597 (U.S.)
T +1-610-481-8565 (other locations)
MondayFriday, 8:00 a.m.5:00 p.m. EST
F 610-481-8690
gastech@airproducts.com

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